New systems for the visible-light-induced polymerization of cationic resins working through a free-radical-promoted process are presented. They are based on a photoinitiator (camphorquinone, isopropylthioxanthone, Eosin), a silane, and a diphenyl iodonium salt, the new compound being the silane. The overall efficiency is strongly affected by the silane structure. The rates of polymerization and final percent conversion are noticeably higher than those obtained in the presence of already studied reference systems. Moreover, contrary to previously investigated free-radical-promoted cationic polymerizations, oxygen does not inhibit the process and an unusual enhancement of the polymerization kinetics is found in aerated conditions: such an observation seems to have never been reported so far. The excited state processes and the role of oxygen as revealed by laser flash photolysis are discussed. The particular behavior of the silyl radicals is outlined. (C) 2008 Wiley Periodicals, Inc.